US5061395A - Hard surface cleaning composition - Google Patents
Hard surface cleaning composition Download PDFInfo
- Publication number
- US5061395A US5061395A US07/461,091 US46109190A US5061395A US 5061395 A US5061395 A US 5061395A US 46109190 A US46109190 A US 46109190A US 5061395 A US5061395 A US 5061395A
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- United States
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000004140 cleaning Methods 0.000 title claims abstract description 44
- -1 NaOH Chemical class 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 18
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 8
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000007859 condensation product Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920000847 nonoxynol Polymers 0.000 claims description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical group CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000003599 detergent Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical class CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SCXCDVTWABNWLW-UHFFFAOYSA-M decyl-dimethyl-octylazanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCC SCXCDVTWABNWLW-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- alkaline compositions have been formulated to eliminate the problems encountered with utilizing acids.
- the alkaline materials raise new problems which have militated against their use commercially.
- the use of alkali metal hydroxides may result in extensive etching of the metal, e.g., aluminum surfaces.
- neutral or alkaline cleaning compositions for metal surfaces including U.S. Pats. Nos. 3,975,215; 4,093,566; and 4,477,290. These patents suggest the use of an alkali metal hydroxide in combination with chelating agents and one or more anionic or nonionic surfactants.
- aqueous cleaning composition comprising a unique combination of chelating agents with a cationic detergent and/or surfactant and one or more nonionic surfactants in an alkaline medium.
- the aqueous cleaning composition of this invention comprises an alkaline aqueous solution having a pH greater than about 7.5, and preferably greater than 9, comprising from about 0.1 to 5.0 parts by weight of a water-soluble cationic surfactant or detergent, 0.1 to 5.0 parts by weight of at least one water-soluble nonionic surfactant, 0.5 to 15 parts by weight of at least one chelating agent, about 10 to 1000 parts, e.g., 50 to 500, by weight of water, and an effective amount of at least one alkaline sodium compound, e.g., 0.1 to 3.0 parts, by weight of sodium hydroxide, sufficient to maintain the aqueous cleaning composition at a pH above about 7.5, and preferably above 9.0.
- This invention relates to a substantially non-streaking alkaline cleaning composition and to the method of using said composition for cleaning hard surfaces, which comprises (a) from about 0.1 to 5.0 parts by weight of at least one water-soluble cationic surface-active agent or detergent, and preferably from about 1.0 to 2.0 parts by weight of at least one water-soluble cationic surfactant or detergent, such as Ethoquad C/25; (b) 0.1 to 5.0 parts by weight, and preferably 0.5 to 2.0 parts by weight of at least one nonionic surfactant, such as the alkylated phenolic ethoxylates; (c) about 0.5 to 15 parts by weight, and preferably from about 2 to 5 parts by weight of at least one chelating agent, such as the sodium salt of nitrilotriacetic acid (NTA) or ethylenediaminetetraacetic acid (EDTA); (d) about 10 to about 1000 parts by weight of water; and (e) an effective amount of at least one alkaline sodium compound, such as
- the alkali metal salts of either ethylenediaminetetraacetic acid or nitrilotriacetic acid are preferably the sodium salt, although the lithium and potassium salts may be employed.
- the salt is either the di, tri, or tetra alkali metal salts, or a mixture thereof.
- ethyleneamine polycarboxylic acids e.g., EDTA and DTA
- EDTA triethylenetetraaminehexaacetic acid
- TPHA tetraethylenepenta amine heptaacetic acid
- nonionic surfactants and/or combinations thereof may be used in the practice of this invention, and include, for example:
- nonionic surfactants may be broadly defined as compounds, aliphatic or alkyl aromatic in nature, which do not ionize in water.
- a well-known class of nonionic synthetic detergents is available under the trade name "TERGITOL.” These compounds are formed by condensing ethylene oxide, alternatively propylene oxide, with an alcohol. The hydrophobic portion of the molecule which exhibits water insolubility has a total carbon chain length of from about 8 to about 20 carbon atoms. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the water solubility of the molecule.
- the method of making these surfactants which comprises reacting the alkylene oxide and the long chain alcohol in the presence of an acid catalyst, is well known.
- Other commercial nonionic surfactants include the Tritons, Tergitols, and Neodols, (which is manufactured by the Shell Oil Co).
- Still other known nonionic surfactants include:
- the polyethylene oxide condensates of alkylphenols the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in amounts equal to about 3 to 25 moles of ethylene oxide per mole of alkylphenol;
- the non-ionic detergent or surfactants used for purposes of this invention belongs to a class of compounds formed by condensation of an alkyl phenol, an alkyl amine, or an aliphatic alcohol with sufficient ethylene oxide to produce a compound having a polyoxyethylene chain within the molecule, i.e., a chain composed of recurring (--O--CH 2 --CH 2 --) groups.
- Many compounds of this type are known and used for their detergent, surface-active, wetting and emulsifying properties.
- the compounds which are useful in the present invention are those produced by condensation of about 4-16, and preferably 4-12 moles, of ethylene oxide with one mole of a compound selected from the group consisting of an alkyl phenol having about 1-15, and preferably 7-10, carbon atoms in the alkyl group; an alkyl amine having about 10-20, and preferably 12-16, carbon atoms in the alkyl group; an aliphatic alcohol having about 10-20, and preferably 12-16, carbon atoms in its molecule; and a hydrophobic group formed by condensing propylene oxide with propylene glycol.
- Mixtures of two or more of the non-ionic detergents or surfactants identified above may also be used.
- the number of moles of ethylene oxide which are condensed with one mole of the compound, i.e., the alkyl phenol, the alkyl amine, or the aliphatic alcohol, depends upon the molecular weight of the hydrophobic portion of the condensation product.
- the non-ionic compound used should have sufficient ethylene oxide units to ensure solubility thereof in the cleaning composition.
- the preferred alkyl phenols which are condensed with ethylene oxide to give a non-ionic detergent useful in the invention are phenols wherein the alkyl group contains about 1-15, and preferably about 7-10, carbon atoms in a straight or branched chain, e.g., saturated or unsaturated.
- the non-ionic detergent is a mixture produced by condensation of 75% of 8-12 moles of ethylene oxide with 1 mole of nonyl phenol and 25% of 4-5 moles of ethylene oxide with 1 mole of nonyl phenol.
- alkylphenol-ethylene oxide condensation products examples include compounds wherein the hydrophobic portion of the product is formed from phenol, methyl phenol (cresol), ethyl phenol, hexyl phenol, octyl phenol, decylphenyl, dodecylphenol, and the like.
- the cationic surface-active agents used in the invention are the quaternary ammonium halide surfactants having the formula: ##STR1##
- R 1 and R 2 are lower (i.e., C 1 -C 7 ) alkyl, and preferably methyl groups
- R3 is a phenyl group or a phenyl group substituted with an alkyl group having about 1-18 carbon atoms or an alkyl group having about 8-20, and preferably 8-18, carbon atoms
- R4 is a phenyl group or a phenyl group substituted with an alkyl group having about 1-18 carbon atoms or an alkyl group having about 8-20, and preferably 8-18, carbon atoms
- X is a halogen, preferably chlorine.
- quaternary ammonium halide surfactants include dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl di-methyl ammonium chloride, (C 12 -C 18 ) n-alkyl dimethyl benzyl ammonium chloride, (C 12 -C 14 ) n-alkyl dimethyl ethylbenzyl ammonium chloride, and dimethyl (difatty) ammonium chloride.
- quaternary ammonium halide surfactants are used as mixtures of about (34% by weight C 12 and 16% by weight C 14 n-alkyl dimethyl ethylbenzyl ammonium chloride, and about (30% by weight C 14 , 15% by weight C 16 , 21/2% by weight C 12 , and 21/2% by weight C 18 ) n-alkyl dimethyl benzyl ammonium chloride, or
- R 1 , R 2 , and R 3 are lower (i.e., C 1 -C 7 ) alkyl, and preferably methyl groups;
- R 4 is an alkyl or phenyl-substituted alkyl group having about 8-20, and preferably 8-18, carbon atoms; and
- X is a halogen, or
- R 1 is an alkyl or phenyl-substituted alkyl group having about 10-20, and preferably 12-16 carbon atoms
- R 2 is lower (i.e., C 1 -C 7 ) alkyl, and preferably a methyl group
- R 3 is [--CH 2 C--H 2 --O--] x H
- R 4 is [--CH 2 CH 2 O--] y H, with the sum of x+y varying between about 2 and 50. Examples of these compounds are those sold by AKZO Chemical Inc. under the trade names Ethoquad 18/12, Ethoquad C/25, and Ethoquad 0/25.
- the pH or alkalinity of the cleaning composition is critical, variations in the pH caused by extraneous factors may require adjustment of the alkalinity.
- the pH is controlled by varying the amount of the potassium or sodium compounds, e.g., sodium or potassium hydroxide and/or sodium carbonate and the like, which is added to the solution to provide a pH at least as high as 7.5, and preferably a pH greater than 9.0, or even higher, ranging from about 11.0 to 12.5.
- inorganic salts which may be used in combination with the alkali metal compounds, e.g., sodium or potassium hydroxide, include sodium carbonate and various mixtures thereof, provided the pH of the cleaning composition is maintained at least above about 7.5.
- the temperature while using the cleaning composition e.g., under pressure from about 10-500 psi, should generally be maintained above freezing, e.g., 35°, and as high as about 200° F., and preferably at temperatures of about 50° F. to 150° F.
- the treatment time will vary, depending upon the nature and condition of the surface being cleaned, and generally will range anywhere from about 5 seconds to 20 minutes, and usually from about 10 seconds to 30 seconds, depending on the temperature and/or pressure at which the cleaner is applied.
- the substrates are rinsed with water to remove soil and cleaning composition.
- the spent solution in rinse waters presents few problems, and therefore can be safely disposed of.
- the salts of the chelating agents are readily biodegraded to relatively harmless components, whereas, the alkaline material in the solution can be neutralized by the addition of various acids until the pH is lowered.
- the soiled surfaces to be cleaned by the composition of this invention include surfaces containing oily or greasy materials and other soils, as well as dust and dirt, etc.
- certain cleaners have extremely good cleaning qualities, they leave undesirable residues, resulting in smears or films. While some cleaners may be fairly non-streaking, it was found that their cleaning capability is limited.
- the cleaning composition of this invention resulted in improved cleaning, including excellent non-streaking and non-film-forming characteristics and necessitating a minimum amount of wiping, if any, due to the combination of the cationic and nonionic surfactants, synergistically functioning with the chelating agent to effectively remove dirt or greasy residues.
- adjuncts such as dies and fragrances and the like which will not deposit on the surfaces
- these ingredients may be added to the aqueous solution in small but effective amounts, if desirable, since water is the principal ingredient of the composition.
- Water is present in the composition in amounts as low as about 10 parts, but can be diluted to as high as 1000 parts, and preferably in the range of about 50 to 500 parts by weight of water, depending on the particular polymeric surfactants and chelant used in the composition.
- the cleaning composition contains from about 50 to 100 parts of water by weight of the total composition.
- the cleaning composition of this invention may be applied to the surface, e.g., metal surfaces, by conventional methods, and particularly on large surfaces, by spraying the cleaner under pressures ranging from about 5 psi to 500 psi.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
This invention relates to an alkaline cleaning composition particularly useful on hard surfaces having a pH greater than 7.5. The cleaning composition comprises a combination of a cationic surfactant and a nonionic surfactant with at least one chelating agent and an alkaline sodium compound, e.g., NaOH, to maintain the aqueous cleaning composition at a pH greater than 7.5.
Description
There are various commercially available hard surface cleaning compositions consisting of small amounts of different surfactants, including nonionic and anionic detergents, solvents such as alcohols, glycol ethers, and alkaline constituents in water. However, the cleaning efficiency of these detergents results in minimal removal of a film thought to be electrostatically held to the hard surface. This film is commonly referred to as "road film" in the industry. Moreover, many of these cleaners necessitate repeated passes with a cleaning cloth or other sorbent to remove this film. Thus, although there are a number of consumer cleaning products, these products require brushing, scrubbing, or some other manual action while the cleaner is in the wet state to achieve effective cleaning. As a consequence, the purpose of this invention is the development of an aqueous cleaning composition which provides good results and requires no manual action other than a high pressure rinse while the cleaner is in the wet state.
For example, attempts to avoid some of these problems are suggested by U.S. Pats. Nos. 4,213,873 and 4,315,828, wherein relatively high molecular weight glycols, e.g., polymeric glycols, are used as a cleaning agent in combination with ammonia hydroxide, alcohols, and water as the solvent. However, to avoid streaking, it was necessary to thoroughly wipe the surface in order to loosen the soil into the cloth; otherwise, a residue generally remained on the surface.
Metal surfaces, and particularly aluminum and aluminum alloys, are presently cleaned with aqueous solutions of acid, including sulfuric acid and hydrofluoric acid, together with one or more surface-active agents or detergents. While these acid solutions are effective and have many advantages, there are many disadvantages associated with acid cleaning. For example, these acids are capable of dissolving most metals commonly utilized in cleaning equipment. Moreover, hydrofluoric acid is particularly unsatisfactory, since the acid and the rinse water containing the acid present environmental problems and are extremely dangerous to personnel.
To avoid the disadvantages of acid cleaners, various alkaline compositions have been formulated to eliminate the problems encountered with utilizing acids. The alkaline materials, however, raise new problems which have militated against their use commercially. For example, the use of alkali metal hydroxides may result in extensive etching of the metal, e.g., aluminum surfaces. There are a number of patents which disclose neutral or alkaline cleaning compositions for metal surfaces, including U.S. Pats. Nos. 3,975,215; 4,093,566; and 4,477,290. These patents suggest the use of an alkali metal hydroxide in combination with chelating agents and one or more anionic or nonionic surfactants.
Accordingly, it is a purpose of this invention to provide an alkaline aqueous cleaning composition useful for cleaning various hard substrates, e.g., metal surfaces.
It is another purpose of this invention to provide a cleaning solution requiring minimal manual action during the cleaning process.
It is still a further purpose of this invention to provide an aqueous cleaning composition comprising a unique combination of chelating agents with a cationic detergent and/or surfactant and one or more nonionic surfactants in an alkaline medium.
It is another purpose of this invention to provide a cleaning composition for cleaning metal substrates wherein the cleaning composition can be sprayed under pressure onto the surface, requiring substantially no additional effort other than a water rinse under pressure of the surface following the application of the cleaning composition.
The aqueous cleaning composition of this invention comprises an alkaline aqueous solution having a pH greater than about 7.5, and preferably greater than 9, comprising from about 0.1 to 5.0 parts by weight of a water-soluble cationic surfactant or detergent, 0.1 to 5.0 parts by weight of at least one water-soluble nonionic surfactant, 0.5 to 15 parts by weight of at least one chelating agent, about 10 to 1000 parts, e.g., 50 to 500, by weight of water, and an effective amount of at least one alkaline sodium compound, e.g., 0.1 to 3.0 parts, by weight of sodium hydroxide, sufficient to maintain the aqueous cleaning composition at a pH above about 7.5, and preferably above 9.0.
This invention relates to a substantially non-streaking alkaline cleaning composition and to the method of using said composition for cleaning hard surfaces, which comprises (a) from about 0.1 to 5.0 parts by weight of at least one water-soluble cationic surface-active agent or detergent, and preferably from about 1.0 to 2.0 parts by weight of at least one water-soluble cationic surfactant or detergent, such as Ethoquad C/25; (b) 0.1 to 5.0 parts by weight, and preferably 0.5 to 2.0 parts by weight of at least one nonionic surfactant, such as the alkylated phenolic ethoxylates; (c) about 0.5 to 15 parts by weight, and preferably from about 2 to 5 parts by weight of at least one chelating agent, such as the sodium salt of nitrilotriacetic acid (NTA) or ethylenediaminetetraacetic acid (EDTA); (d) about 10 to about 1000 parts by weight of water; and (e) an effective amount of at least one alkaline sodium compound, such as 0.1 to 3.0 parts of sodium hydroxide, to maintain the aqueous solution at a pH above about 7.5, and preferably above 9.0.
The alkali metal salts of either ethylenediaminetetraacetic acid or nitrilotriacetic acid are preferably the sodium salt, although the lithium and potassium salts may be employed. The salt is either the di, tri, or tetra alkali metal salts, or a mixture thereof. While the lower molecular weight ethyleneamine polycarboxylic acids, e.g., EDTA and DTA, are useful for purposes of this invention, it is also possible to utilize the higher molecular weight compounds, such as triethylenetetraaminehexaacetic acid (TTHA), and the higher molecular weight compounds such as tetraethylenepenta amine heptaacetic acid (TTPHA), either alone or in combination, with other known polycarboxylic acid chelating agents.
The following nonionic surfactants and/or combinations thereof may be used in the practice of this invention, and include, for example:
(a) nonylphenoxy polyethoxy ethanol (sold by Rohm and Haas Co. under the trademark "TRITON" N 100);
(b) modified polyethoxy adduct (sold by Rohm and Haas Co. under the trademark "TRITON" CF 76);
(c) an alkyl polyethoxylated ether (sold by Jefferson Chemical Co. under the trademark "SURFONIC" LF 17);
(d) a modified ethoxylated straight chain alcohol (sold by BASF Wyandotte Corp. under the trademark "PLURAFAC" D-25);
(e) an ethoxylated abietic acid derivative (sold by Hercules, Inc. under the trademark "SURFACTANT AR 150"); and/or
(f) block copolymers of about 90% polyoxypropylene and about 10% polyoxyethylene (sold by BASF Wyandotte Corp. under the trademark "PLURONIC" 31R1).
These nonionic surfactants may be broadly defined as compounds, aliphatic or alkyl aromatic in nature, which do not ionize in water. For example, a well-known class of nonionic synthetic detergents is available under the trade name "TERGITOL." These compounds are formed by condensing ethylene oxide, alternatively propylene oxide, with an alcohol. The hydrophobic portion of the molecule which exhibits water insolubility has a total carbon chain length of from about 8 to about 20 carbon atoms. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the water solubility of the molecule. The method of making these surfactants, which comprises reacting the alkylene oxide and the long chain alcohol in the presence of an acid catalyst, is well known. Other commercial nonionic surfactants include the Tritons, Tergitols, and Neodols, (which is manufactured by the Shell Oil Co).
Still other known nonionic surfactants include:
(g) the polyethylene oxide condensates of alkylphenols; the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in amounts equal to about 3 to 25 moles of ethylene oxide per mole of alkylphenol; and
(h) the condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., an alcoholethylene oxide condensate having from about 3 to 30 moles of ethylene oxide per mole of alcohol, the alcohol fraction having from 10 to 14 carbon atoms.
In general, the non-ionic detergent or surfactants used for purposes of this invention belongs to a class of compounds formed by condensation of an alkyl phenol, an alkyl amine, or an aliphatic alcohol with sufficient ethylene oxide to produce a compound having a polyoxyethylene chain within the molecule, i.e., a chain composed of recurring (--O--CH2 --CH2 --) groups. Many compounds of this type are known and used for their detergent, surface-active, wetting and emulsifying properties. The compounds which are useful in the present invention are those produced by condensation of about 4-16, and preferably 4-12 moles, of ethylene oxide with one mole of a compound selected from the group consisting of an alkyl phenol having about 1-15, and preferably 7-10, carbon atoms in the alkyl group; an alkyl amine having about 10-20, and preferably 12-16, carbon atoms in the alkyl group; an aliphatic alcohol having about 10-20, and preferably 12-16, carbon atoms in its molecule; and a hydrophobic group formed by condensing propylene oxide with propylene glycol. Mixtures of two or more of the non-ionic detergents or surfactants identified above may also be used. The number of moles of ethylene oxide which are condensed with one mole of the compound, i.e., the alkyl phenol, the alkyl amine, or the aliphatic alcohol, depends upon the molecular weight of the hydrophobic portion of the condensation product. The non-ionic compound used should have sufficient ethylene oxide units to ensure solubility thereof in the cleaning composition.
The preferred alkyl phenols which are condensed with ethylene oxide to give a non-ionic detergent useful in the invention are phenols wherein the alkyl group contains about 1-15, and preferably about 7-10, carbon atoms in a straight or branched chain, e.g., saturated or unsaturated. In a particularly preferred embodiment, the non-ionic detergent is a mixture produced by condensation of 75% of 8-12 moles of ethylene oxide with 1 mole of nonyl phenol and 25% of 4-5 moles of ethylene oxide with 1 mole of nonyl phenol. Examples of other alkylphenol-ethylene oxide condensation products are compounds wherein the hydrophobic portion of the product is formed from phenol, methyl phenol (cresol), ethyl phenol, hexyl phenol, octyl phenol, decylphenyl, dodecylphenol, and the like.
The cationic surface-active agents used in the invention are the quaternary ammonium halide surfactants having the formula: ##STR1##
(a) wherein R1 and R2 are lower (i.e., C1 -C7) alkyl, and preferably methyl groups; R3 is a phenyl group or a phenyl group substituted with an alkyl group having about 1-18 carbon atoms or an alkyl group having about 8-20, and preferably 8-18, carbon atoms; R4 is a phenyl group or a phenyl group substituted with an alkyl group having about 1-18 carbon atoms or an alkyl group having about 8-20, and preferably 8-18, carbon atoms; and X is a halogen, preferably chlorine. Examples of suitable quaternary ammonium halide surfactants include dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl di-methyl ammonium chloride, (C12 -C18) n-alkyl dimethyl benzyl ammonium chloride, (C12 -C14) n-alkyl dimethyl ethylbenzyl ammonium chloride, and dimethyl (difatty) ammonium chloride. Particularly preferred examples of quaternary ammonium halide surfactants are used as mixtures of about (34% by weight C12 and 16% by weight C14 n-alkyl dimethyl ethylbenzyl ammonium chloride, and about (30% by weight C14, 15% by weight C16, 21/2% by weight C12, and 21/2% by weight C18) n-alkyl dimethyl benzyl ammonium chloride, or
(b) wherein R1, R2, and R3 are lower (i.e., C1 -C7) alkyl, and preferably methyl groups; R4 is an alkyl or phenyl-substituted alkyl group having about 8-20, and preferably 8-18, carbon atoms; and X is a halogen, or
(c) wherein R1 is an alkyl or phenyl-substituted alkyl group having about 10-20, and preferably 12-16 carbon atoms; R2 is lower (i.e., C1 -C7) alkyl, and preferably a methyl group; R3 is [--CH2 C--H2 --O--]x H and R4 is [--CH2 CH2 O--]y H, with the sum of x+y varying between about 2 and 50. Examples of these compounds are those sold by AKZO Chemical Inc. under the trade names Ethoquad 18/12, Ethoquad C/25, and Ethoquad 0/25.
Since the pH or alkalinity of the cleaning composition is critical, variations in the pH caused by extraneous factors may require adjustment of the alkalinity. The pH is controlled by varying the amount of the potassium or sodium compounds, e.g., sodium or potassium hydroxide and/or sodium carbonate and the like, which is added to the solution to provide a pH at least as high as 7.5, and preferably a pH greater than 9.0, or even higher, ranging from about 11.0 to 12.5.
Other inorganic salts which may be used in combination with the alkali metal compounds, e.g., sodium or potassium hydroxide, include sodium carbonate and various mixtures thereof, provided the pH of the cleaning composition is maintained at least above about 7.5. The temperature while using the cleaning composition, e.g., under pressure from about 10-500 psi, should generally be maintained above freezing, e.g., 35°, and as high as about 200° F., and preferably at temperatures of about 50° F. to 150° F. The treatment time will vary, depending upon the nature and condition of the surface being cleaned, and generally will range anywhere from about 5 seconds to 20 minutes, and usually from about 10 seconds to 30 seconds, depending on the temperature and/or pressure at which the cleaner is applied. Following the cleaner application, the substrates are rinsed with water to remove soil and cleaning composition. The spent solution in rinse waters presents few problems, and therefore can be safely disposed of. For example, the salts of the chelating agents are readily biodegraded to relatively harmless components, whereas, the alkaline material in the solution can be neutralized by the addition of various acids until the pH is lowered.
The soiled surfaces to be cleaned by the composition of this invention include surfaces containing oily or greasy materials and other soils, as well as dust and dirt, etc. In many instances, while certain cleaners have extremely good cleaning qualities, they leave undesirable residues, resulting in smears or films. While some cleaners may be fairly non-streaking, it was found that their cleaning capability is limited. The cleaning composition of this invention, however, resulted in improved cleaning, including excellent non-streaking and non-film-forming characteristics and necessitating a minimum amount of wiping, if any, due to the combination of the cationic and nonionic surfactants, synergistically functioning with the chelating agent to effectively remove dirt or greasy residues.
In addition to the combination of the surfactants, i.e., the cationic and nonionic surfactants and the chelating agents, other adjuncts, such as dies and fragrances and the like which will not deposit on the surfaces, may be used in the aqueous composition. These ingredients may be added to the aqueous solution in small but effective amounts, if desirable, since water is the principal ingredient of the composition.
Water is present in the composition in amounts as low as about 10 parts, but can be diluted to as high as 1000 parts, and preferably in the range of about 50 to 500 parts by weight of water, depending on the particular polymeric surfactants and chelant used in the composition. Optimally, the cleaning composition contains from about 50 to 100 parts of water by weight of the total composition.
The following illustrates a typical cleaning composition for purposes of this invention.
______________________________________
EXAMPLE 1
Components Parts by Weight
______________________________________
Water 10-1000
Nitrilotriaacetic acid
0.5-15
(sodium salt)
Soda ash ph of 9
(sodium carbonate)
Caustic soda ph of 9
(sodium hydroxide)
Nonylphenol ethoxylates
0.1-5.0
Quaternary ammonium halide
0.1-5.0
(Ethoquad C/25)
______________________________________
The cleaning composition of this invention may be applied to the surface, e.g., metal surfaces, by conventional methods, and particularly on large surfaces, by spraying the cleaner under pressures ranging from about 5 psi to 500 psi.
While this invention has been described by way of a number of specific embodiments, it is obvious that there are other variations or modifications which can be used without departing from the spirit and scope of the invention set forth in the appended claims.
Claims (11)
1. An alkaline aqueous cleaning composition for hard surfaces consisting of
0.1 to 5.0 parts by weight of a water-soluble quaternary ammonium halide,
0. 1 to 5.0 parts by weight of at least one non-ionic surfactant derived from the condensation of an alkyl phenol or aliphatic alcohol and an alkylene oxide,
0.5 to 15 parts by weight of at least one water-soluble chelating agent,
10 to 1000 parts by weight of water, and
an effective amount of at least one alkaline inorganic sodium compound to maintain the aqueous cleaning solution at a pH above 7.5.
2. A process for cleaning a hard surface which comprises applying to said surface an aqueous cleaning composition having a water temperature above about 35° F. at pressures ranging from about 10-500 psi; said cleaning composition consisting of 0.1 to 5.0 parts by weight of a water-soluble quaternary ammonium halide,
0.1 to 5.0 parts by weight of at least one non-ionic surfactant derived from the condensation of an alkyl phenol or aliphatic alcohol and an alkylene oxide,
0.5 to 15 parts by weight of at least one water-soluble alkaline metal salt of a lower molecular weight carboxylic acid,
10 to 1000 parts by weight of water, and
an effective amount of at least one alkaline sodium compound to maintain the cleaning solution at a pH above 7.5.
3. The composition of claim 1 wherein the cationic surfactant is present in an amount of about 1.0 to 2.0 parts by weight, the nonionic surfactant is present in an amount of about 0.5 to 2.0 parts by weight, the chelating agent is present in an amount of about 0.5 to 15 parts by weight, and the water is present in an amount ranging from about 50 to 500 parts by weight.
4. The composition of claim 1 wherein the sodium compound comprises sodium hydroxide.
5. The composition of claim 1 wherein the non-ionic surfactant is a condensation product of ethylene oxide and an alkylphenol.
6. The composition of claim 5 wherein the condensation product is a nonylphenol ethoxylate.
7. The composition of claim 6 wherein at least one of the chelating agents is nitrilotriaacetic acid.
8. The composition of claim 7 wherein the chelating agent is a mixture of nitrilotriaacetic acid and ethylenediaminetetraacetic acid.
9. The composition of claim 8 wherein the cationic surfactant is a quaternary ammonium halide and the non-ionic surfactant is a condensation product of ethylene oxide and an alkylphenol.
10. The composition of claim 9 wherein the alkaline sodium compound is a combination of sodium hydroxide and sodium carbonate and the pH of the solution is maintained above 9.0.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/461,091 US5061395A (en) | 1990-01-04 | 1990-01-04 | Hard surface cleaning composition |
| KR1019920701591A KR927003778A (en) | 1990-01-04 | 1990-10-11 | Hard Surface Cleaning Composition |
| PCT/US1990/005841 WO1991009930A1 (en) | 1990-01-04 | 1990-10-11 | Hard surface cleaning composition |
| AU67447/90A AU6744790A (en) | 1990-01-04 | 1990-10-11 | Hard surface cleaning composition |
| JP3500380A JP2800846B2 (en) | 1990-01-04 | 1990-10-11 | Hard surface cleaning composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/461,091 US5061395A (en) | 1990-01-04 | 1990-01-04 | Hard surface cleaning composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5061395A true US5061395A (en) | 1991-10-29 |
Family
ID=23831192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/461,091 Expired - Lifetime US5061395A (en) | 1990-01-04 | 1990-01-04 | Hard surface cleaning composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5061395A (en) |
| JP (1) | JP2800846B2 (en) |
| KR (1) | KR927003778A (en) |
| AU (1) | AU6744790A (en) |
| WO (1) | WO1991009930A1 (en) |
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| JP3022054B2 (en) * | 1993-05-28 | 2000-03-15 | 朝日化学工業株式会社 | Detergent composition and cleaning method |
| GB9503594D0 (en) * | 1995-02-23 | 1995-04-12 | Unilever Plc | Cleaning composition comprising dialkyl cationic surfactants |
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| WO1995035359A1 (en) * | 1994-06-20 | 1995-12-28 | Arne Pedersen | Aqueous cleaning composition |
| US6284723B1 (en) | 1995-07-26 | 2001-09-04 | Boli Zhou | Antimicrobial hard surface cleaner |
| US6200941B1 (en) | 1995-09-06 | 2001-03-13 | S. C. Johnson & Son, Inc. | Fully diluted hard surface cleaners containing high concentrations of certain anions |
| WO1998055173A1 (en) | 1997-06-04 | 1998-12-10 | Advanced Cardiovascular Systems, Inc. | Steerable guidewire with enhanced distal support |
| US7455646B2 (en) | 1997-06-04 | 2008-11-25 | Advanced Cardiovascular Systems, Inc. | Polymer coated guide wire |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO1991009930A1 (en) | 1991-07-11 |
| JPH05502683A (en) | 1993-05-13 |
| AU6744790A (en) | 1991-07-24 |
| JP2800846B2 (en) | 1998-09-21 |
| KR927003778A (en) | 1992-12-18 |
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